US5015329A - Pre-swelling and etching of plastics for plating - Google Patents
Pre-swelling and etching of plastics for plating Download PDFInfo
- Publication number
- US5015329A US5015329A US07/489,366 US48936690A US5015329A US 5015329 A US5015329 A US 5015329A US 48936690 A US48936690 A US 48936690A US 5015329 A US5015329 A US 5015329A
- Authority
- US
- United States
- Prior art keywords
- polycarbonate
- etching
- swelling
- polymer
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000005530 etching Methods 0.000 title claims abstract description 87
- 229920003023 plastic Polymers 0.000 title description 30
- 239000004033 plastic Substances 0.000 title description 28
- 238000007747 plating Methods 0.000 title description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000004417 polycarbonate Substances 0.000 claims abstract description 112
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 106
- 229920000642 polymer Polymers 0.000 claims abstract description 73
- 239000002904 solvent Substances 0.000 claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- 239000000080 wetting agent Substances 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- -1 alkylene glycols Chemical class 0.000 claims description 21
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 14
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 13
- 150000007513 acids Chemical class 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 5
- 230000003301 hydrolyzing effect Effects 0.000 claims 2
- 239000000463 material Substances 0.000 claims 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000003673 urethanes Chemical class 0.000 claims 1
- 230000008961 swelling Effects 0.000 abstract description 74
- 239000003795 chemical substances by application Substances 0.000 abstract description 50
- 238000009472 formulation Methods 0.000 abstract description 29
- 230000015556 catabolic process Effects 0.000 abstract description 24
- 238000006731 degradation reaction Methods 0.000 abstract description 24
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 150000002739 metals Chemical class 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 59
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 18
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 18
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000002202 Polyethylene glycol Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 229940092714 benzenesulfonic acid Drugs 0.000 description 10
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 10
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 10
- 150000008282 halocarbons Chemical class 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 150000007530 organic bases Chemical class 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000002203 pretreatment Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 230000003381 solubilizing effect Effects 0.000 description 5
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 235000019743 Choline chloride Nutrition 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 229960003872 benzethonium Drugs 0.000 description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 3
- 229960003178 choline chloride Drugs 0.000 description 3
- 229940075419 choline hydroxide Drugs 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- SIYLLGKDQZGJHK-UHFFFAOYSA-N dimethyl-(phenylmethyl)-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]ammonium Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 SIYLLGKDQZGJHK-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical class OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- POJXMQFERGRXMG-UHFFFAOYSA-N 2,2,2-tris(2-methoxyethoxy)ethanamine Chemical compound COCCOC(CN)(OCCOC)OCCOC POJXMQFERGRXMG-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YZGQDNOIGFBYKF-UHFFFAOYSA-N Ethoxyacetic acid Chemical compound CCOCC(O)=O YZGQDNOIGFBYKF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 2
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 2
- 229960000228 cetalkonium chloride Drugs 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002780 morpholines Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000004901 trioxanes Chemical class 0.000 description 2
- CSVFWMMPUJDVKH-UHFFFAOYSA-N 1,1-dichloropropan-2-one Chemical compound CC(=O)C(Cl)Cl CSVFWMMPUJDVKH-UHFFFAOYSA-N 0.000 description 1
- MBNMGGKBGCIEGF-UHFFFAOYSA-N 1,1-diethoxypropane Chemical compound CCOC(CC)OCC MBNMGGKBGCIEGF-UHFFFAOYSA-N 0.000 description 1
- UIOXNNAWANDJCZ-UHFFFAOYSA-N 1,1-dimethoxypropane Chemical compound CCC(OC)OC UIOXNNAWANDJCZ-UHFFFAOYSA-N 0.000 description 1
- AGYUOJIYYGGHKV-UHFFFAOYSA-N 1,2-bis(2-chloroethoxy)ethane Chemical compound ClCCOCCOCCCl AGYUOJIYYGGHKV-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- HUTXVUPGARJNHM-UHFFFAOYSA-N 1-(2-chloroethoxy)ethanol Chemical compound CC(O)OCCCl HUTXVUPGARJNHM-UHFFFAOYSA-N 0.000 description 1
- QKDPDTZVDBRIFG-UHFFFAOYSA-N 1-(methylamino)-3-phenylpropan-2-ol Chemical compound CNCC(O)CC1=CC=CC=C1 QKDPDTZVDBRIFG-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- CUZLJOLBIRPEFB-UHFFFAOYSA-N 1-methoxypropan-2-one Chemical compound COCC(C)=O CUZLJOLBIRPEFB-UHFFFAOYSA-N 0.000 description 1
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- GFISDBXSWQMOND-UHFFFAOYSA-N 2,5-dimethoxyoxolane Chemical compound COC1CCC(OC)O1 GFISDBXSWQMOND-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- LECMBPWEOVZHKN-UHFFFAOYSA-N 2-(2-chloroethoxy)ethanol Chemical compound OCCOCCCl LECMBPWEOVZHKN-UHFFFAOYSA-N 0.000 description 1
- XGLVDUUYFKXKPL-UHFFFAOYSA-N 2-(2-methoxyethoxy)-n,n-bis[2-(2-methoxyethoxy)ethyl]ethanamine Chemical compound COCCOCCN(CCOCCOC)CCOCCOC XGLVDUUYFKXKPL-UHFFFAOYSA-N 0.000 description 1
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 description 1
- YOIQWFZSLGRZJX-UHFFFAOYSA-N 2-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC=C1O YOIQWFZSLGRZJX-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- KECMLGZOQMJIBM-UHFFFAOYSA-N 2-[2-(2-chloroethoxy)ethoxy]ethanol Chemical compound OCCOCCOCCCl KECMLGZOQMJIBM-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- JTQOSVROGSRLHJ-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;calcium Chemical compound [Ca].OCCN(CCO)CCO JTQOSVROGSRLHJ-UHFFFAOYSA-N 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- OAQYRNDEOJQVBN-UHFFFAOYSA-N 5-(diethylamino)pentan-2-ol Chemical compound CCN(CC)CCCC(C)O OAQYRNDEOJQVBN-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- DCOSGYUTUVBSCY-UHFFFAOYSA-N CN(C)C1N(CCOC1)CC Chemical compound CN(C)C1N(CCOC1)CC DCOSGYUTUVBSCY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- MLLOCBIXMBXZCN-UHFFFAOYSA-M [OH-].COCCOCC[N+](CC)(CCOCCOC)CCOCCOC Chemical compound [OH-].COCCOCC[N+](CC)(CCOCCOC)CCOCCOC MLLOCBIXMBXZCN-UHFFFAOYSA-M 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- JABXMSSGPHGCII-UHFFFAOYSA-N acetic acid;propane-1,2-diol Chemical compound CC(O)=O.CC(O)CO JABXMSSGPHGCII-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical compound CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229940115457 cetyldimethylethylammonium bromide Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229950006187 hexamethonium bromide Drugs 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002485 inorganic esters Chemical class 0.000 description 1
- 231100000647 material safety data sheet Toxicity 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- ARMLJSXXXFXSLQ-UHFFFAOYSA-L trimethyl-[10-(trimethylazaniumyl)decyl]azanium;diiodide Chemical compound [I-].[I-].C[N+](C)(C)CCCCCCCCCC[N+](C)(C)C ARMLJSXXXFXSLQ-UHFFFAOYSA-L 0.000 description 1
- FAPSXSAPXXJTOU-UHFFFAOYSA-L trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;dibromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C FAPSXSAPXXJTOU-UHFFFAOYSA-L 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
Definitions
- This invention relates to formulations and processes for swelling, etching and plating for decorative and functional purposes of plastics of functionalized polymers, suitably those having at least one hydrolyzable functionality such as anhydride, carbonate, ester (carboxyl and sulfonic), amide, urethane and imide.
- the polymer could be a copolymer and/or an alloy of two or more polymers.
- the invention is of particular value with poly(oxy-carbonyloxy-1,4-phenylene-isopropylidene-1,4-phenylene), referred herein as polycarbonate and/or PC.
- the etching formulations utilize at least one swelling agent and at least one degradation agent.
- the etched surface can be plated with electroless nickel or copper with satisfactory adhesion of the plated metals.
- Polymeric plastics are plated for decorative and functional reasons such as decoration and electromagnetic interference (EMI) shielding.
- EMI electromagnetic interference
- electronic equipment which can generate frequency between 10 4 to 10 9 (10,000 to 10 billion) cycles per second should be shielded.
- the most widely used plastic for housing electronic devices is polycarbonate.
- Polycarbonate is generally unaffected by aqueous solution of etchants and hence requires pre-swelling.
- the terms, swelling, pre-swelling, pre-etching, pre-conditioning, and pre-treatment are used interchangeably herein.
- polymers having hydroxylatable functionalities such as polycarbonate have tough surfaces. They cannot be sufficiently etched with common aqueous etchants such as aqueous chromic acid or aqueous alkali metal hydroxides. Pre-swelling is required for fast etching.
- polycarbonate is not soluble in a number of common organic solvents.
- the good or “fast” solvents are those in which it is highly soluble at room temperature.
- the “poor”, “slow” or “minor roughening” solvents are those in which it has limited solubility at room temperature.
- the nonsolvents are those in which it is insoluble.
- PC Preswollen PC is easy to degrade as the swelling provides a higher surface area and porous surface. As a result, the etching/degradation is rapid.
- the roughened surface also provides a strong mechanical bonding between the plastic and the plated metals to be plated thereon.
- Degradation of PC provides polar functionalities such as --OH and --COOH on the micro-roughened surface which, in turn, provides a wettable surface. Such a wettable surface is required for electroless plating of metals as all commercially available plating baths are aqueous.
- pre-swelling system uses toxic halocarbon solvents for pre-swelling and is frequently followed by chromic acid as an etchant.
- chromic acid as an etchant.
- the pre-swelling system offered by Shipley Inc. (according to the Material Safety Data Sheet of Shipley for PM-921 Conditioner) uses dichloropropanol to pre-etch polycarbonate.
- halocarbons can undergo dehydrohalogenation and oxidation, it is difficult to prepare a stable bath containing a mixture of halocarbon (as pre-etch) with either a strong base etchant or with chromic acid which is a strong oxidizing agent.
- chromic acid is toxic, expensive, produces a toxic fumes.
- recovery of chromium and waste disposal of chromium (sludge) is expensive.
- alkali metal hydroxides have been used for etching polycarbonate, they are not very effective in providing a surface with satisfactory properties for electroless plating. The use of mixtures of swelling agents (and/or solubilizing agents) and degradation agents as etching systems for polycarbonate has not been reported.
- U.S. Pat. No. 3,649,391 describes a process for producing a marking receptive (pre-swelling/etching) surface of polystyrene by action of a solution of chloromethane, perchloroethylene, and heptane.
- the claimed formulations can be used for polystyrene only.
- polyepoxy is swollen with solvents such as methylethyl ketone, tetrahydrofuran, dioxane and like.
- solvents such as methylethyl ketone, tetrahydrofuran, dioxane and like.
- Processes of pre-swelling polyamides with aqueous solution of oragnic acids such as trichloroacetic acid and other chlorinated solvents such as dichloropropanol are described in U.S. Pat. Nos. 4,125,649 and 4,335,164.
- U.S. Pat. No. 4,125,649 also include formulations containing water miscible halocarbons for pre-swelling followed by etching with chromic acid.
- the prior art describes neither (1) etching of polycarbonate in one step nor (2) etching of polycarbonate in two steps (pre-swelling) followed by degradation wherein polycarbonate is degraded (etched) with a solution containing a solubilizing agent, and/or a wetting agent and a base. Etching pre-swollen polycarbonate with mineral acids other than chromic acid is also not taught.
- plastics of functionalized polymers having at least one hydrolyzable functionality such as anhydride, ester (carboxyl and sulfonic), amide, urethane and imide, preferably polycarbonate
- the etched surface provides satisfactory adhesion of electroless nickel or copper.
- a solubilizing agent is used to increase the miscibility of degradation and swelling agents.
- the polymers can be swollen and etched in one bath by using a mixture of swelling (or wetting agent) and degradation agents or with a compound having the ability to swell and etch the polymers simultaneously.
- swelling and degradation is done separately.
- the plastic surface is swollen and etched with mineral acids followed by treatment with a base.
- a water miscible swelling agent is preferred for pre-swelling polycarbonate. If the swelling agent is not itself miscible with water, or if it does not dissolve the selected basic degradation agent, it can be made miscible or a solvator by addition of a solubilizing agent.
- Some representative functional groups which rapidly swell polymers such as polycarbonate include: Ether (--O--), halocarbon (X--C, where X is a halogen radical), and aromatic compounds. Certain ketones, acetals and ketals can also swell polycarbonate. Aliphatic ethers are the preferred class of compounds for swelling polycarbonate and other plastics mainly because some of them are water soluble and are stable to bases.
- Alkyl ethers and substituted alkyl ethers such as halo- or hydroxy-substituted alkyl ethers including ethers of alkylene glycols, arylethers, arylalkylethers, cyclic ethers and their derivatives.
- halo- or hydroxy-substituted alkyl ethers including ethers of alkylene glycols, arylethers, arylalkylethers, cyclic ethers and their derivatives.
- aryl moieties phenyl, suitably substituted phenyl may be used.
- solvents such as propanediol dimethylether, ethoxyacetic acid, methoxyethylether, 2-(2-aminoethoxy)ethanol, 1,2-bis(2-chloroethoxy)ethane, 1,4-butanediol diglycidyl ether, 2-(2-n-butoxyethoxy)ethanol, 2-(2-chloroethoxy)ethanol, 2-[2-(2-chloroethoxy)ethoxy]ethanol, diethylene glycol dibutyl ether, 2-(2-ethoxy ethoxy)ethanol, 2-ethoxyethyl ether, ethylene glycol dimethyl ether, diethyleneglycol dimethylether, dipropylene glycol dimethylether, 2-methoxyethylether (diglyme), dimethoxy propane, ethoxy ethylether, butylphenylether, 2-(2-methoxyethoxy)ethanol, tetraethylene glycol dimethylether, triethylene glycol dimethylether and
- Cyclic ethers and their derivatives such as benzofuran, butanediol diglycidyl ether, dioxane and substituted dioxanes, trioxanes and substituted trioxanes, furans, furfuryl alcohol, morpholines and substituted morpholines such as dimethylamino ethylmorpholine, ethylmorpholine, 4-morpholineethane sulfonic acid, 4-methylmorpholine-N-oxide), tetrahydrofuran and substituted tetrahydrofurans such as dimethoxy hydrofuran or dimethoxy tetrahydrofuran.
- Aldehydes, ketones, acetals and ketals derived from lower alkanols and lower alkanoic acids of 1 to 6 carbon atoms or phenyl lower alkanols or lower alkanoic acids Included in this category are phenylacetaldehyde, glyceraldehyde, benzylacetone, dichloroacetone, methoxyacetone, benzophenone, propionaldehyde diethyl acetal, dioxolane, and trioxane may also be used.
- Water miscible halocarbons which can be used as swelling agents include mono-and poly-, chloro- and fluoro-substituted derivatives of acetone, acetic acid, butanol, ethanol, and propanol.
- a good solvent can be made poor by adding a miscible nonsolvent and vice versa.
- a compound can be used as solubilizing agent if it is soluble in the swelling agent and a nonsolvent (such as water) selected to convert a "good" swelling agent to a “poor” one.
- Organic compounds having --OH, --COOH, --SO 3 H, --NH--, --NH 2 , --NR 3 , --N + R 4 and other polar functionalities can act as solublizing agents.
- ethanol, glycerols, acetic acid, and benzene sulfonic acid can be used as solublizing agents.
- chloroform and dichloromethane have ability to swell polycarbonate but they are not miscible with water. When methanol is added to an immiscible mixture of chloroform and water, a clear solution is obtained which has ability to swell polycarbonate.
- alkanolamines and phenolamines such as benzyl-N-methylethanolamine, diethylaminophenol, 2-[(2-dimethylamino)ethyl]methyl aminoethanol, ethanolamine, diethanolamine, dimethyethanolamine, butyldi-ethanolamine, triethanolamine, 5-diethylamino-2-pentanol, diethyl-ethanolamine, dialkoxybenzene, dimethylaminopropanol, dimethylethanolamine, chloroethoxyethanol, tetra kis(2-hydroxyethyl)ethylenediamine, tripentaerythritol, 2,4,6-tris(dimethylaminomethyl)phenol.
- alkanolamines and phenolamines such as benzyl-N-methylethanolamine, diethylaminophenol, 2-[(2-dimethylamino)ethyl]methyl aminoethanol, ethanolamine, diethanolamine, dimethyethanolamine, butyldi-
- Tertiary amines such as pyridine and substituted pyridines for example dialkylaminopyridines, aniline and substituted anilines, for example dialkylanilines, hexamethylenetetraamine, tetramethylethylenediamine, tetraethylenepropanediamine.
- Ether-amines such as tris(2-methoxyethoxyethyl)amine, benzethonium, 4(2-dimethylamino)ethylmorpholine, glycerol, isopropanol, acetic acid, palmitic acid, benzoic acid, benzene sulfonic acid and dimethylformamide.
- wetting agents may permit an inactive etchant to become active.
- Wetting agents are inherently soluble in the inactive solvent. Thus, while they act like solubilizing agents, they cannot be so designated.
- wetting agents are triethanolamine and glycerol which activate aqueous sodium hydroxide. For example, aqueous NaOH does not etch swollen polycarbonate very effectively, even at high concentration and temperature.
- triethanolamine calcium solubilizing agent which also acts as wetting agent in this case allows NaOH to etch swollen polycarbonate very effectively at room temperature and at lower concentration of NaOH.
- swelling agents which are normally insoluble in water can be used for pre-swelling polycarbonate and other plastics by using appropriate solublizing agents.
- solublizing agents for plastic is widened.
- a solubilizing agent can also be a swelling agent and viceversa.
- triethyleneglycol dimethylether is a good swelling agent. It can also be used as a solubilizing or wetting agent.
- Certain compounds may be used ether as solubilizing agents or as poor solvents (useful swelling agents), for example: 2-butoxyethanol, 2-(2-butoxy ethoxy)ethanol, diethyleneglycol, monoethers of ethylene glycols, propylglycols, and glycerol, ethoxyethanol, 2(2-ethoxyethoxy)ethanol, ethers of tetraethyleneglycol, benzethonium and tetrabutylphosphoniumbromide.
- Nonsolvents which convert "good” solvents to “poor” solvents may or may not require the use of a solubilizing agent.
- a solubilizing agent In addition to water, there include mono- and polyhydric alcohols which, preferably do not carry halo or ether functions.
- Other suitable nonsolvents include alkanols and glycols of 1-20 carbon atoms.
- inorganic nonsolvents such as water and phosphoric acid.
- Organic nonsolvents such as hydrocarbons, suitably alkanes and phenyl alkanes of 6 to 20 carbon atoms such as: decane, toluene, xylene, etc.; alkanoic acids, suitably acetic acid, decanoic acid, citric acid, etc.; alcohols suitably lower mono and polyhydric alkanols including sugars and phenols, these are exemplified by ethanol, isopropanol, glycerol, glucose, phenol, etc.; high molecular weight amides of more than 6 carbon atoms such as octadecanamide; high molecular weight amines such as dodecyleamine; high molecular weight ketones, such as butanone, octanone; and high molecular weight esters, such as butyl acetate, dimethyloxylate.
- the invention is not limited to swelling agents which are liquid at room temperature.
- a compound which is solid at room temperature but either can be dissolved in water or other solvents can also be used as swelling agent.
- a compound which has low melting point, e.g. below 150° C. can also be used in the present invention.
- the swelling bath can be prepared by melting the compound and maintaining the bath above the melting temperature.
- Certain compounds have the ability to swell polycarbonate and also have acid or base functionality. Thus, they can simultaneously act as swelling agents as well as degradation agents. These groups of compounds should have at least one or more of the following functionalities for swelling polymer and degradation of carbonate functionality:
- Compounds having functional groups such as --SO 3 H, and --N + R 4 OH can cause degradation of polycarbonate. Under suitable conditions, e.g., with appropriate swelling agent and high temperature, polycarbonate can also be degraded by primary (R--NH 2 ), secondary amines (R--NH--R), tertiary amines (NR 3 ) and carboxylic acids (R--COOH) wherein R is alkyl, aralkyl or aryl.
- Aryl sulfonic acids which can be mono-, ortho-, meta- and para-substituted di; and tri-substituted benzene sulfonic acids, and naphthalene sulfonic acids are especially suitable.
- Compounds having ether and N + --OH functionality can also swell and etch PC, such as tris(2-methoxy ethoxyethyl)ethyl ammonium hydroxide are especially suitable.
- molten benzene sulfonic acid acts as a solvent to swell polycarbonate.
- the sulfonic acid group has ability to hydrolyze the carbonate functionality thereby degrading polycarbonate.
- the surface of polycarbonate becomes wettable and provides acceptable adhesion of electroless nickel, after immersion in molten benzene sulfonic acid.
- Benzene sulfonic acid diluted with inorganic liquids such as water, sulfuric acid and phosphoric acid or diluted with organic liquids such as ethers are essentially unaffected by benezene sulfonic acid, can be used as pre-etching systems.
- the pre-etching can be controlled by diluting benzene sulfonic acid.
- Preferred diluents are water and aqueous sulfuric acid.
- polycarbonate After pre-etching with the benezene sulfonic acid, polycarbonate can be etched with an inorganic or organic base such as sodium hydroxide or tetraethylammonium hydroxide. As shown, polycarbonate plaques pre-etched with benezene sulfonic acid followed by etching sodium hydroxide can be satisfactorily plated with electroless nickel.
- an inorganic or organic base such as sodium hydroxide or tetraethylammonium hydroxide.
- Preferred degradation agents include quaternary ammonium hydroxides such as tetraethylammonium hydroxide and choline hydroxide.
- a mixture of quaternary ammonium salts such as tetraethylammonium chloride and/or choline chloride and alkali metal hydroxide such as KOH are also desirable degradation agents.
- the most preferred degradation agents are alkali metal hydroxide.
- aqueous solutions of alkali metal hydroxides are not very effective in etching polycarbonate, unless solvated with a solubilizing agent and/or wetting agent.
- the swelling agent For the one-step process the swelling agent must be stable to the base used for degradation of polycarbonate. However, stability to a base is not required for the two- and three-step etching process. In the latter cases, compounds such as inorganic and organic esters, for example, ethylacetate, glycol acetate, propylene glycol acetate, cellusolve acetate, and like can be used for pre-swelling.
- the two-step process for swelling, followed by etching of polycarbonate is also equally desirable.
- the one-step swelling/etching solutions can also be used as etchant solution in two-step etching process.
- better adhesion of electroless metal is expected because the plastic is already pre-swollen and hence etching could be faster and smoother.
- pre-etching and etching are preferred to be carried out at room temperature, higher and lower temperatures can be used. If the reaction is fast at RT, lower temperature can be employed and vice versa.
- the swelling and etching formulations and processes described here are not limited to polycarbonate. They can be used for a number of other plastics having at least one hydrolyzable functionalities such as anhydride, ester (carboxyl and sulfonic), amide, urethane and immide.
- the polymer could be a copolymer and/or an alloy of two or more polymers).
- 1b--Accelerator 100 ml. of Enplate Accelerator 860 (Supplied by Enthone, Inc.) was mixed with 900 ml. of deonized water to make the accelerator bath. The catalyzed parts were immersed in the accelerator bath for 8-15 minutes, usually 10 minutes, at room temperature. After rinsing the parts with water, they were immersed in either electroless nickel or electroless copper baths described below:
- Cross-Hatch test The plated metal coat was cut crosswise with a cross-cut tool (Precision Gage & Tool Company, Dayton, Ohio) using the procedure described in ASTM method #D3359. One end of Scotch (cellophane) tape was firmly applied on the cross-hatch. The tape was pulled from the other end. The adhesion was rated as below:
- Solubilizing agent 50 ml. of methanol added to above solution.
- This mixture swells and etches polycarbonate.
- the etched surface is wettable.
- Polymer Polycarbonate (Laxan) plaque.
- Polymer Polycarbonate (Laxan) plaque.
- Etch Formulation 1:1 aqueous KOH:isopropanol, 20 minutes, at RT
- Polymer Polycarbonate (Laxan) plaque.
- Etch Formulation 10% solution of tetraethyl ammonium hydroxide in ethanol:water (90:10), 20 minutes, at RT
- Electroless Nickel As described in Example 1.
- Polymer Polycarbonate (Laxan) plaque.
- Etch Formulation 20% aqueous solution of tetraethyl ammonium hydroxide 20 minutes, at RT.
- Electroless Nickel As described in Example 1.
- Polymer Polycarbonate (Laxan) plaque.
- Etch Formulation Sulfuric (50 ml.) plus phosphoric (50 ml.) plus 1 ml. nitric (other ranges are: sulfuric 30-80%, phosphoric 0-50%, nitric 0.1 to 10%, and water - Balance).
- Electroless Nickel As described in Example 1.
- Etch Formulation Sulfuric (50 ml.) plus phosphoric (50 ml.) plus 1 ml. nitric (other ranges are: sulfuric 30-80%, phosphoric 0-50%, nitric 0.1 to 10%, and water - Balance).
- Electroless Nickel As in Example 1.
- Adhesion of electroless nickel Passes the cross-hatch test and improves upon storage at RT or upon annealing at higher temperatures, e.g., 80° C. for one hour.
- Plated samples need annealing to improve the adhesion of electroless nickel.
- Electroless Nickel As in Example 1.
- Pre-etch Formulation Shipley PM 921 (prepared from dichloro propanol):Water (80:120 v/v,) 5 minutes at 45° C.
- Etch #1 Formulation Sulfuric (55 ml.), and phosphoric (45 ml.) 10 minutes at RT
- Electroless Nickel As in Example 1.
- Etch Formulation 20% Tetraethylammonium hydroxide in water 5 minutes at RT
- Electroless Nickel As in Example 1.
- Pre-etch Formulation Shipley PM 921:water (80:120), 10 minutes at 45° C.
- Etch Formulation 25 ml of 20% Tetraethylammonium hydroxide in water.
- Electroless copper As in Example 1.
- Pre-etch Formulation Shipley PM 921:water (2:3), 10 minutes at 45° C.
- Etch Formulation 25 ml. of 20% Tetraethylammonium hydroxide in water and 10 ml. of isopropanol, 10 minutes at 45° C.
- Electroless Copper As in Example 1.
- Swelling/Etching Solution Triethyelene glycol dimethyl ether:polyethyelene glycol (mol. wt. 200):tetraethylammonium hydroxide 25% solution (1:1:1) at 25° C. for 5 minutes.
- Electroless Nickel As described in Example 1.
- Electroless Nickel As described in Example 1.
- Electroless Nickel As described in Example 1.
- Step 1 Shipley pre-etch. 6 minutes at 45° C.
- Step 2 20% tetraethylammonium hydroxide in water at 60° C. for 5 minutes.
- Electroless copper As described in Example 1.
- Step 1 Shipley pre-etch. 6 minutes at 45° C.
- Step 2 20% choline hydroxide in water at 60° C. for 5 minutes.
- Electroless copper As described in Example 1.
- Step 1 Shipley pre-etch. 6 minutes at 45° C.
- Step 2 15% tetraethylammonium bromide+15% sodium hydroxide in water at 60° C. for 5 minutes.
- Electroless copper As described in Example 1.
- Step 1 Shipley pre-etch. 6 minutes at 45° C.
- Step 2 15% Choline chloride+15% sodium hydroxide in water at 60° C. for 5 minutes.
- Electroless copper As described in Example 1.
- Electroless copper As described in Example 1.
- Step 1 8:2 triethyleneglycol dimethylether:water, 5 minutes at RT
- Step 2 10:2.5:2 Aqueous 10% NaOH:Triethylene glycol dimethyl ether:polyethylene glycol (mol. wt. 200), 5 minutes at RT
- Electroless Nickel As described in Example 1.
- Pre-etching System Benzene sulfonic acid at 65° C.
- Benzene sulfonic acid provides wettable surface.
- the wettable surface can be plated with electroless nickel and copper with good adhesion.
- Benzene sulfonic acid provides wettable surface.
- the wettable surface can be plated with electroless nickel and copper.
- Step 1 Enthone pre-etch 3489, 10 minutes at 45° C.
- Step 2 50 ml 25% NaOH+25 ml triethanolamine, 5 minutes at RT
- Etching Solution Triethanolamine:Triethyelene glycol dimethylether:NaOH:water (2.5:4:1.5:10 v/v/w/v) at 50° C. for 5 minutes.
- Electroless Nickel As described in example 1
- Polymer Polycarbonate (Laxan FL-900 and 920A) panels
- Etching Solution Water:NaOH:Triethanolamine:Ethyleneglycol dimethylether (120:15:28:37 w:w:w:w) at 50° C. for 10 minutes
- Electroless Nickel As described in Example 1.
- Electroless Nickel As described in Example 1.
- Electroless Nickel As described in Example 1.
- Electroless Nickel As described in Example 1.
- Electroless Nickel As described in Example 1.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Formulations are provided for pre-swelling and etching of functionalized polymers, such as polycarbonate in two or three steps. The etched surface can then be plated with electroless nickel or copper with satisfactory adhesion of the plated metals. Swelling agents make polymer molecules on and near the surface of the polymer easily accessible to a degradation agent. A degradation agent degradates the polymer molecules. If required, a solubilizing agent increases the miscibility of the degradation agent and the swelling agent. A wetting agent increases the effectiveness of the etching agent. In a two-step process, polymer parts are first treated with a solution of a swelling agent followed by etching with a solution of degradation agent.
Description
This application is a continuation of application Ser. No. 07/268,154, filed 11/7/88 now U.S. Pat. No. 4,941,940.
This invention relates to formulations and processes for swelling, etching and plating for decorative and functional purposes of plastics of functionalized polymers, suitably those having at least one hydrolyzable functionality such as anhydride, carbonate, ester (carboxyl and sulfonic), amide, urethane and imide. The polymer could be a copolymer and/or an alloy of two or more polymers. The invention is of particular value with poly(oxy-carbonyloxy-1,4-phenylene-isopropylidene-1,4-phenylene), referred herein as polycarbonate and/or PC. The etching formulations utilize at least one swelling agent and at least one degradation agent. The etched surface can be plated with electroless nickel or copper with satisfactory adhesion of the plated metals.
General art of etching and plating of plastics, including formulations and processes is described in a number of books and reviews including: 1. Guidebook Directory, Metals and Plastics Publications, Inc., Hackensack, N.J. 1988; 2. Standards and Guidelines for Electroplated Plastics, American Society of Electroplated Plastics, Englewood Cliffs, N.J. 1984; 3. Metallic Coating of Plastics, W. Goldie, Electrochemical Publication Ltd., Hatch End, England, 1968; and 4. Electroplating of Plastics, I. R. Weiner, Finishing Publications Ltd., Hampton Hill, England, 1977. Plastic parts are subjected to the following major processes to plate them: pre-swelling (if required), etching, neutralizing, catalyzation, acceleration, electroless plating and electroplating. The details of these processes and formulations are given in the above references.
Polymeric plastics are plated for decorative and functional reasons such as decoration and electromagnetic interference (EMI) shielding. In order to prevent EMI from escaping the source and protect sensitive electronic equipment from outside EMI sources, electronic equipment which can generate frequency between 104 to 109 (10,000 to 10 billion) cycles per second should be shielded. The most widely used plastic for housing electronic devices is polycarbonate. Polycarbonate is generally unaffected by aqueous solution of etchants and hence requires pre-swelling. The terms, swelling, pre-swelling, pre-etching, pre-conditioning, and pre-treatment are used interchangeably herein.
Many polymers having hydroxylatable functionalities, such as polycarbonate have tough surfaces. They cannot be sufficiently etched with common aqueous etchants such as aqueous chromic acid or aqueous alkali metal hydroxides. Pre-swelling is required for fast etching. In particular, polycarbonate is not soluble in a number of common organic solvents. The good or "fast" solvents are those in which it is highly soluble at room temperature. The "poor", "slow" or "minor roughening" solvents are those in which it has limited solubility at room temperature. The nonsolvents are those in which it is insoluble.
Good solvents usually cause excessive swelling, hence a surface which is very rough and unsuitable for subsequent plating. If transparent plastic is used, it becomes essentially opaque. With poor solvents which cause a proper degree of swelling, the surface is uniformly micro-roughened and can be plated. If transparent plastic is used, it becomes translucent in a poor solvent. This properly swollen surface is required for proper etching and plating of plastics. Nonsolvents do not swell the plastic and hence there can be no adhesion for plating. Thus, if a transparent sheet is used, it remains transparent.
Preswollen PC is easy to degrade as the swelling provides a higher surface area and porous surface. As a result, the etching/degradation is rapid. The roughened surface also provides a strong mechanical bonding between the plastic and the plated metals to be plated thereon. Degradation of PC provides polar functionalities such as --OH and --COOH on the micro-roughened surface which, in turn, provides a wettable surface. Such a wettable surface is required for electroless plating of metals as all commercially available plating baths are aqueous.
One pre-swelling system available commercially, uses toxic halocarbon solvents for pre-swelling and is frequently followed by chromic acid as an etchant. For example, the pre-swelling system offered by Shipley Inc., (according to the Material Safety Data Sheet of Shipley for PM-921 Conditioner) uses dichloropropanol to pre-etch polycarbonate.
There is a need for a nontoxic solvent for pre-etching polycarbonate. There is also a need for a etching system for polycarbonate which is nontoxic and provides excellent adhesion of electroless copper or nickel (at least as good as that obtained with chromic acid). In order to reduce the cost due to drag out and save time, it is desirable to utilize one bath to simultaneously achieve swelling and etching of polycarbonate.
As halocarbons can undergo dehydrohalogenation and oxidation, it is difficult to prepare a stable bath containing a mixture of halocarbon (as pre-etch) with either a strong base etchant or with chromic acid which is a strong oxidizing agent. In addition, chromic acid is toxic, expensive, produces a toxic fumes. Furthermore, recovery of chromium and waste disposal of chromium (sludge) is expensive. While alkali metal hydroxides have been used for etching polycarbonate, they are not very effective in providing a surface with satisfactory properties for electroless plating. The use of mixtures of swelling agents (and/or solubilizing agents) and degradation agents as etching systems for polycarbonate has not been reported.
A number of patents have been issued on swelling, etching, and plating of plastics. Most of these patents relate to etching of ABS (a coplymer of acrylonitrile, butadiene, and styrene) with chromic acid. There are several patents on pre-swelling and non-chromic acid etching.
U.S. Pat. No. 3,649,391 describes a process for producing a marking receptive (pre-swelling/etching) surface of polystyrene by action of a solution of chloromethane, perchloroethylene, and heptane. The claimed formulations can be used for polystyrene only. U.S. Pat. Nos. 3,660,293, 3,671,289, 3,795,622 and 4,281,034 describe processes of increasing adhesion of electroless metals by pre-swelling ABS with aqueous solutions of hydroxylated and etherified monoacetate, e.g., glycol diacetate and cellusolve acetate; five membered heterocyclic compounds such as propylene carbonate and mixture of halocarbons and etchanol. These patents do not describe the art of pre-swelling polycarbonate or other plastics. A method of increasing adhesion of polyepoxy is presented in U.S. Pat. No. 3,758,332. The surface of polyepoxy is swollen with solvents such as methylethyl ketone, tetrahydrofuran, dioxane and like. Processes of pre-swelling polyamides with aqueous solution of oragnic acids such as trichloroacetic acid and other chlorinated solvents such as dichloropropanol are described in U.S. Pat. Nos. 4,125,649 and 4,335,164. U.S. Pat. No. 4,125,649 also include formulations containing water miscible halocarbons for pre-swelling followed by etching with chromic acid.
A published patent application (PCT Int. Appl. No. 86/US/1199, Jan. 15, 1987) to C. Courduvelis and D. E. Stone, describes formulations and processes of pre-swelling plastics such as polyether polyimide with solvents such as dimethylsulfoxide, propanediol ether, followed by etching with chromic acid.
The prior art describes neither (1) etching of polycarbonate in one step nor (2) etching of polycarbonate in two steps (pre-swelling) followed by degradation wherein polycarbonate is degraded (etched) with a solution containing a solubilizing agent, and/or a wetting agent and a base. Etching pre-swollen polycarbonate with mineral acids other than chromic acid is also not taught.
We have found that plastics of functionalized polymers having at least one hydrolyzable functionality such as anhydride, ester (carboxyl and sulfonic), amide, urethane and imide, preferably polycarbonate, can be swollen and etched for plating by certain swelling agents and degradation agents, in one, two or three steps. The etched surface provides satisfactory adhesion of electroless nickel or copper. If required, a solubilizing agent is used to increase the miscibility of degradation and swelling agents. The polymers can be swollen and etched in one bath by using a mixture of swelling (or wetting agent) and degradation agents or with a compound having the ability to swell and etch the polymers simultaneously. In the two-step process, swelling and degradation is done separately. In the three-step process, the plastic surface is swollen and etched with mineral acids followed by treatment with a base.
A water miscible swelling agent is preferred for pre-swelling polycarbonate. If the swelling agent is not itself miscible with water, or if it does not dissolve the selected basic degradation agent, it can be made miscible or a solvator by addition of a solubilizing agent.
Some representative functional groups which rapidly swell polymers such as polycarbonate include: Ether (--O--), halocarbon (X--C, where X is a halogen radical), and aromatic compounds. Certain ketones, acetals and ketals can also swell polycarbonate. Aliphatic ethers are the preferred class of compounds for swelling polycarbonate and other plastics mainly because some of them are water soluble and are stable to bases.
The following is a non-limiting list of some representative classes of compounds and specific examples of such "good solvents".
Alkyl ethers and substituted alkyl ethers, such as halo- or hydroxy-substituted alkyl ethers including ethers of alkylene glycols, arylethers, arylalkylethers, cyclic ethers and their derivatives. Preferably there are used lower alkyl and lower alkylene moieties of 1-20 and 2-20 carbon atoms respectively. As aryl moieties, phenyl, suitably substituted phenyl may be used. Specific examples include solvents such as propanediol dimethylether, ethoxyacetic acid, methoxyethylether, 2-(2-aminoethoxy)ethanol, 1,2-bis(2-chloroethoxy)ethane, 1,4-butanediol diglycidyl ether, 2-(2-n-butoxyethoxy)ethanol, 2-(2-chloroethoxy)ethanol, 2-[2-(2-chloroethoxy)ethoxy]ethanol, diethylene glycol dibutyl ether, 2-(2-ethoxy ethoxy)ethanol, 2-ethoxyethyl ether, ethylene glycol dimethyl ether, diethyleneglycol dimethylether, dipropylene glycol dimethylether, 2-methoxyethylether (diglyme), dimethoxy propane, ethoxy ethylether, butylphenylether, 2-(2-methoxyethoxy)ethanol, tetraethylene glycol dimethylether, triethylene glycol dimethylether and polyethylene glycol. Benzylether, phenylether, benzoxybenzyl alcohol, methoxybenzyl alcohol. Cyclic ethers and their derivatives, such as benzofuran, butanediol diglycidyl ether, dioxane and substituted dioxanes, trioxanes and substituted trioxanes, furans, furfuryl alcohol, morpholines and substituted morpholines such as dimethylamino ethylmorpholine, ethylmorpholine, 4-morpholineethane sulfonic acid, 4-methylmorpholine-N-oxide), tetrahydrofuran and substituted tetrahydrofurans such as dimethoxy hydrofuran or dimethoxy tetrahydrofuran.
Aldehydes, ketones, acetals and ketals derived from lower alkanols and lower alkanoic acids of 1 to 6 carbon atoms or phenyl lower alkanols or lower alkanoic acids. Included in this category are phenylacetaldehyde, glyceraldehyde, benzylacetone, dichloroacetone, methoxyacetone, benzophenone, propionaldehyde diethyl acetal, dioxolane, and trioxane may also be used.
Water miscible halocarbons which can be used as swelling agents include mono-and poly-, chloro- and fluoro-substituted derivatives of acetone, acetic acid, butanol, ethanol, and propanol. A good solvent can be made poor by adding a miscible nonsolvent and vice versa.
A compound can be used as solubilizing agent if it is soluble in the swelling agent and a nonsolvent (such as water) selected to convert a "good" swelling agent to a "poor" one. Organic compounds having --OH, --COOH, --SO3 H, --NH--, --NH2, --NR3, --N+ R4 and other polar functionalities can act as solublizing agents. For example, ethanol, glycerols, acetic acid, and benzene sulfonic acid can be used as solublizing agents. For example, chloroform and dichloromethane have ability to swell polycarbonate but they are not miscible with water. When methanol is added to an immiscible mixture of chloroform and water, a clear solution is obtained which has ability to swell polycarbonate.
Especially desirable as solubilizing and swelling agents are alkanolamines and phenolamines such as benzyl-N-methylethanolamine, diethylaminophenol, 2-[(2-dimethylamino)ethyl]methyl aminoethanol, ethanolamine, diethanolamine, dimethyethanolamine, butyldi-ethanolamine, triethanolamine, 5-diethylamino-2-pentanol, diethyl-ethanolamine, dialkoxybenzene, dimethylaminopropanol, dimethylethanolamine, chloroethoxyethanol, tetra kis(2-hydroxyethyl)ethylenediamine, tripentaerythritol, 2,4,6-tris(dimethylaminomethyl)phenol. Tertiary amines such as pyridine and substituted pyridines for example dialkylaminopyridines, aniline and substituted anilines, for example dialkylanilines, hexamethylenetetraamine, tetramethylethylenediamine, tetraethylenepropanediamine. Ether-amines such as tris(2-methoxyethoxyethyl)amine, benzethonium, 4(2-dimethylamino)ethylmorpholine, glycerol, isopropanol, acetic acid, palmitic acid, benzoic acid, benzene sulfonic acid and dimethylformamide.
The addition of certain compounds, designated as wetting agents may permit an inactive etchant to become active. Wetting agents are inherently soluble in the inactive solvent. Thus, while they act like solubilizing agents, they cannot be so designated. Examples of such wetting agents are triethanolamine and glycerol which activate aqueous sodium hydroxide. For example, aqueous NaOH does not etch swollen polycarbonate very effectively, even at high concentration and temperature. However, an aqueous solution of triethanolamine calcium solubilizing agent which also acts as wetting agent in this case allows NaOH to etch swollen polycarbonate very effectively at room temperature and at lower concentration of NaOH.
It is quite likely that some swelling agents may form an emulsion. Such emulsions can be destroyed to form a clear solution for pre-swelling polycarbonate by adding a solubilizing and/or a wetting agent.
Thus, swelling agents which are normally insoluble in water can be used for pre-swelling polycarbonate and other plastics by using appropriate solublizing agents. Thus the choice for selection of swelling agents for plastic is widened.
There is no sharp line of demarcation between swelling agents, wetting agents and solubilizing agents. A solubilizing agent can also be a swelling agent and viceversa. For example, triethyleneglycol dimethylether is a good swelling agent. It can also be used as a solubilizing or wetting agent.
Certain compounds may be used ether as solubilizing agents or as poor solvents (useful swelling agents), for example: 2-butoxyethanol, 2-(2-butoxy ethoxy)ethanol, diethyleneglycol, monoethers of ethylene glycols, propylglycols, and glycerol, ethoxyethanol, 2(2-ethoxyethoxy)ethanol, ethers of tetraethyleneglycol, benzethonium and tetrabutylphosphoniumbromide.
Nonsolvents which convert "good" solvents to "poor" solvents, may or may not require the use of a solubilizing agent. In addition to water, there include mono- and polyhydric alcohols which, preferably do not carry halo or ether functions. Other suitable nonsolvents include alkanols and glycols of 1-20 carbon atoms.
As nonsolvents, there may be specifically recited: inorganic nonsolvents such as water and phosphoric acid. Organic nonsolvents such as hydrocarbons, suitably alkanes and phenyl alkanes of 6 to 20 carbon atoms such as: decane, toluene, xylene, etc.; alkanoic acids, suitably acetic acid, decanoic acid, citric acid, etc.; alcohols suitably lower mono and polyhydric alkanols including sugars and phenols, these are exemplified by ethanol, isopropanol, glycerol, glucose, phenol, etc.; high molecular weight amides of more than 6 carbon atoms such as octadecanamide; high molecular weight amines such as dodecyleamine; high molecular weight ketones, such as butanone, octanone; and high molecular weight esters, such as butyl acetate, dimethyloxylate. Some of the nonsolvents such as triethanolamine, can also be solubilizing agents or wetting agents.
The invention is not limited to swelling agents which are liquid at room temperature. A compound which is solid at room temperature but either can be dissolved in water or other solvents can also be used as swelling agent. A compound which has low melting point, e.g. below 150° C. can also be used in the present invention. The swelling bath can be prepared by melting the compound and maintaining the bath above the melting temperature.
Certain compounds have the ability to swell polycarbonate and also have acid or base functionality. Thus, they can simultaneously act as swelling agents as well as degradation agents. These groups of compounds should have at least one or more of the following functionalities for swelling polymer and degradation of carbonate functionality:
Compounds having functional groups such as --SO3 H, and --N+ R4 OH can cause degradation of polycarbonate. Under suitable conditions, e.g., with appropriate swelling agent and high temperature, polycarbonate can also be degraded by primary (R--NH2), secondary amines (R--NH--R), tertiary amines (NR3) and carboxylic acids (R--COOH) wherein R is alkyl, aralkyl or aryl. Aryl sulfonic acids which can be mono-, ortho-, meta- and para-substituted di; and tri-substituted benzene sulfonic acids, and naphthalene sulfonic acids are especially suitable. Compounds having ether and N+ --OH functionality can also swell and etch PC, such as tris(2-methoxy ethoxyethyl)ethyl ammonium hydroxide are especially suitable.
For example, molten benzene sulfonic acid acts as a solvent to swell polycarbonate. The sulfonic acid group has ability to hydrolyze the carbonate functionality thereby degrading polycarbonate. The surface of polycarbonate becomes wettable and provides acceptable adhesion of electroless nickel, after immersion in molten benzene sulfonic acid.
Benzene sulfonic acid diluted with inorganic liquids such as water, sulfuric acid and phosphoric acid or diluted with organic liquids such as ethers are essentially unaffected by benezene sulfonic acid, can be used as pre-etching systems. The pre-etching can be controlled by diluting benzene sulfonic acid. Preferred diluents are water and aqueous sulfuric acid.
After pre-etching with the benezene sulfonic acid, polycarbonate can be etched with an inorganic or organic base such as sodium hydroxide or tetraethylammonium hydroxide. As shown, polycarbonate plaques pre-etched with benezene sulfonic acid followed by etching sodium hydroxide can be satisfactorily plated with electroless nickel.
Representative examples of quaternary ammonium compounds which can be used as degradation agents alone or with alkali metal hydroxides are Aliquot, benzalkonium chloride, benzylcetyldimethylammonium chloride, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, cetyldimethylethylammonium bromide, cetyltrimethylammonium bromide, choline chloride, choline hydroxide, tetraethylammonium bromide, tetraethylammonium hydroxide, benzyltriethylammonium chloride, and benzyltrimethylammonium hydroxide, betaine, decamethylenebis(trimethylammonium iodide), cetyltrimethylammonium bromide, hexamethonium bromide, methyltributylammonium chloride, phenyltrimethylammonium chloride, benzyltributylammonium chloride, benzyltrimethylammonium chloride, benzethonium, benzyldimethylsterylammonium chloride and benzylcetyldimethylammonium chloride.
Preferred degradation agents include quaternary ammonium hydroxides such as tetraethylammonium hydroxide and choline hydroxide. A mixture of quaternary ammonium salts such as tetraethylammonium chloride and/or choline chloride and alkali metal hydroxide such as KOH are also desirable degradation agents.
The most preferred degradation agents are alkali metal hydroxide. However, aqueous solutions of alkali metal hydroxides are not very effective in etching polycarbonate, unless solvated with a solubilizing agent and/or wetting agent.
For the one-step process the swelling agent must be stable to the base used for degradation of polycarbonate. However, stability to a base is not required for the two- and three-step etching process. In the latter cases, compounds such as inorganic and organic esters, for example, ethylacetate, glycol acetate, propylene glycol acetate, cellusolve acetate, and like can be used for pre-swelling.
While the one-step swelling/etching process is especially preferred, the two-step process for swelling, followed by etching of polycarbonate, is also equally desirable.
The one-step swelling/etching solutions can also be used as etchant solution in two-step etching process. In such case, better adhesion of electroless metal is expected because the plastic is already pre-swollen and hence etching could be faster and smoother. For better control of the etching process, one may reduce the concentration of the swelling agent in the etching solution. There is no sharp line of demarcation between the swelling/etching solution of one-step process and the etching solution of the two-step process.
Though pre-etching and etching are preferred to be carried out at room temperature, higher and lower temperatures can be used. If the reaction is fast at RT, lower temperature can be employed and vice versa.
The swelling and etching formulations and processes described here are not limited to polycarbonate. They can be used for a number of other plastics having at least one hydrolyzable functionalities such as anhydride, ester (carboxyl and sulfonic), amide, urethane and immide. (The polymer could be a copolymer and/or an alloy of two or more polymers).
The following examples are illustrative of carrying out the claimed invention but should not be construed as being limitation on the scope or spirit of the instant invention.
Hereinbelow, unless stated to the contrary, all ratios and percentages are v/v.
After preswelling and/or etching the polycarbonate parts with the formulations and processes described in Examples 15 to 40, they were plated with electroless copper or nickel using the formulations and processes described below:
1a--Catalyst: 120 ml. of 12N HCl was mixed with 880 ml. of deionized water. To this acid solution was added 40 ml. of Enplate 443 solution (supplied by Enthone INC., New Haven, Conn.) to make the catalyst bath. Etched parts were rinsed with water and immersed in the catalyst bath for 4-8 minutes, usually 6 minutes, at room temperature. The parts were rinsed with water before immersing in the accelerator bath.
1b--Accelerator: 100 ml. of Enplate Accelerator 860 (Supplied by Enthone, Inc.) was mixed with 900 ml. of deonized water to make the accelerator bath. The catalyzed parts were immersed in the accelerator bath for 8-15 minutes, usually 10 minutes, at room temperature. After rinsing the parts with water, they were immersed in either electroless nickel or electroless copper baths described below:
1c--Electroless Nickel: To 898 ml. of deionized water 47 ml. of Enplate Ni 880A (supplied by Enthone Inc.) was added. To the mixture, 55 ml. of Enplate Ni 880B solution (supplied by Enthone, Inc.) was added. The pH of the bath was adjusted to 9 with ammonium hydroxide. The plastic parts were immersed in this bath for 8 to 20 minutes at room temperature.
1d--Electroless Copper: To 560 ml. of deionized water, 80 ml. of Enplate Cu-404A and 160 ml of Enplate Cu-404B (both supplied by Enthone, Inc.) were added. The plastic parts were immersed in this bath for 8 to 120 minutes at room temperature.
Pre-etched, etched and plated polycarbonate parts were tested using the following methods:
2a--Pre-etch test: The pre-etch usually swells plastic and hence the smooth surface of the plastic becomes rough and deglazed. The degree of swelling was estimated qualitatively as follows:
Excessive Swelling: Very rough surface. Transparent sheets become essentially opaque.
Proper Swelling: Moderately micro-roughened surface. Transparent sheets become translucent.
Poor Swelling: Smooth surface. Surface remains essentially unaffected. Transparent sheets remain transparent.
2b--Etching test: Surface wettable with water. A thin layer of water remains on the etched surface.
2c--Adhesion of Electroless metals: Adhesion of electroless nickel and copper was tested using the cross-hatch and thermal cycle tests.
Cross-Hatch test: The plated metal coat was cut crosswise with a cross-cut tool (Precision Gage & Tool Company, Dayton, Ohio) using the procedure described in ASTM method #D3359. One end of Scotch (cellophane) tape was firmly applied on the cross-hatch. The tape was pulled from the other end. The adhesion was rated as below:
Satisfactory: A few cross hatched pieces peel (flake) off. If proper experimental conditions of pre-etching, etching and plating are used, the satisfactory plating can become good or excellent plating.
Acceptable: No flaking off of cross-hatched pieces, but some peeling of metal occurs at crosscuts. If proper experimental conditions of pre-etching, etching and plating are used, the acceptable plating can become good or excellent plating.
Good: No flaking off of any kind.
Excellent: No flaking even after thermal cycle.
Thermal cycling: Polycarbonate parts were placed in steam autoclave for 20 minutes at 110° C. and 12 psi pressure. The parts are then cooled to room temperature. If the adhesion of plated metals is good or excellent, the plated metal does not blister or plate separation does not occur.
Polymer: Transparent polycarbonate (Laxan) sheet
Solution: Triethylene glycol dimethylether
Results: The sheet becomes opaque in 30 seconds. Nonwettable surface, indicative of unetched surface.
Polymer: Transparent polycarbonate (Laxan) sheet
Solution: Triethylene glycol dimethylether: water (8:2)
Results: The surface gets roughened in 10 minutes. Nonwettable surface.
Polymer: Transparent polycarbonate (Laxan) sheet
Solution: Polyethyleneglycol methylether, molecular weight=350.
Results: Damages (deglazes) the surface in 5 minutes at room temperature. Nonwettable surface.
Polymer: Transparent polycarbonate (Laxan) sheet
Solution: Polyethyleneglycol methylether (molecular weight=350):water (7:2)
Results: No noticeable damage at RT for 5 minutes.
Polymer: Transparent polycarbonate (Laxan) sheet
Solution: Polyethyleneglycol (mol.wt.=200)
Results: No noticeable damage at RT for 30 minutes.
Polymer: Transparent polycarbonate (Laxan) sheet
______________________________________ Time (min.) Liquid of immersion Clarity Swellability ______________________________________ EGDME 1 Opaque Good EGDME:Water 2 Translucent Poor (8.2) EG:DME:Water 5 Transparent Bad (5.5) EE 30 Transparent Bad EG 30 Transparent None ______________________________________ EGDME = Ethylene glycol dimethylether, EE = Ethoxy ethanol. EG = Ethylene glycol, Temperature was room temperature.
Polymer: Polycarbonate (Laxan) plaque
Solution: Triethylene glycol dimethylether:isopropanol:tetraethylammonium hydroxide 25% solution (2:1:1) at room temperature for 5 minutes.
Results: Roughens the surface and surface is wettable.
Polymer: Polycarbonate (Laxan) plaque
Solution: As in Example 9 but at 60° C. (Triethylene glycol dimethylether:isopropanol:tetraethylammonium hydroxide 25% solution (2:1:1) at 60° C. for 5 minutes).
Results: Highly roughened and wettable surface.
Polymer: Polycarbonate
Solution: 40 ml. of chloroform and 10 ml. of water
Result: An immiscible mixture
Solubilizing agent: 50 ml. of methanol added to above solution.
Results: The immiscible mixture forms a clear solution upon addition of methanol (solubilizing agent). This solution swells polycarbonate.
Polymer: Polycarbonate (Laxan) plaque
Solution: 10 ml. of 10% aqueous solution of NaOH plus 2.5 ml. of Shipley's preconditioner (PM-921 Conditioner) which contains of water and dichloropropanol.
Results: Two layers are formed.
Solubilizing agent: 5 ml. of polyethylene glycol (mol. wt.=200) added to the above mixture.
Results: A clear single phase solution is obtained.
(NOTE: A mixture of alkali and halogenated solvent is not desirable in practice).
Polymer: Polycarbonate (Laxan) plaque
Solution: 10 ml. of 10% NaOH and 2.5 ml. triethylene glycol dimethyl ether.
Results: Two layers are formed.
Solubilizing agent: 2 ml. of polyethylene glycol (mol. wt.=200) added to the above mixture.
Results: A clear single phase solution is obtained.
This mixture swells and etches polycarbonate. The etched surface is wettable.
Polymer: Polycarbonate (Laxan) plaque
Solution: Polyethylene glycol methyl ether (molecular weight=350):water:10% NaOH (7:2:1)
Results: Polymer swells and etches in 5 minutes at RT.
Polymer: Polycarbonate (Laxan) plaque.
Pre-treatment: None.
Etch Formulation: 6N Aqueous solution of KOH 20 minutes, at RT
Electroless Nickel: As described in Example 1
Results: The surface remains unaffected. Nonwettable surface. Very poor adhesion of electroless nickel.
Polymer: Polycarbonate (Laxan) plaque.
Pre-treatment: None.
Etch Formulation: 1:1 aqueous KOH:isopropanol, 20 minutes, at RT
Electroless Nickel: As described in Example 1
Results: The surface remains unaffected. Nonwettable surface. Poor adhesion of electroless nickel.
Polymer: Polycarbonate (Laxan) plaque.
Pre-treatment: None.
Etch Formulation: 10% solution of tetraethyl ammonium hydroxide in ethanol:water (90:10), 20 minutes, at RT
Electroless Nickel: As described in Example 1.
Results: The surface remains unaffected. Nonwettable surface. Poor adhesion of electroless nickel.
Polymer: Polycarbonate (Laxan) plaque.
Pre-treatment: None.
Etch Formulation: 20% aqueous solution of tetraethyl ammonium hydroxide 20 minutes, at RT.
Electroless Nickel: As described in Example 1.
Results: The surface remains unaffected. Nonwettable Surface. Poor adhesion of electroless nickel.
Polymer: Polycarbonate (Laxan) plaque.
Pre-treatment: None.
Etch Formulation: Sulfuric (50 ml.) plus phosphoric (50 ml.) plus 1 ml. nitric (other ranges are: sulfuric 30-80%, phosphoric 0-50%, nitric 0.1 to 10%, and water - Balance).
Time: 5 and 10 minutes at RT.
Comments: The etched surface was not very wettable.
Electroless Nickel: As described in Example 1.
Results: Poor adhesion of electroless nickel.
Polymer: Polycarbonate (Laxan)
Pre-etch: Enplate 3489:Water (75:25 v/v) (made from an ether)
Temperature: 75° C. (Temperature range: 25°-85° C.)
Time: 7 minutes (Time range tried: 3-10 minutes)
Etch Formulation: Sulfuric (50 ml.) plus phosphoric (50 ml.) plus 1 ml. nitric (other ranges are: sulfuric 30-80%, phosphoric 0-50%, nitric 0.1 to 10%, and water - Balance).
Time: 10 minutes (Other ranges: 3-30 minutes)
Temperature: RT (Other ranges: 25° to 85° C.)
Electroless Nickel: As in Example 1.
Results: Adhesion of electroless nickel: Passes the cross-hatch test and improves upon storage at RT or upon annealing at higher temperatures, e.g., 80° C. for one hour.
Comments: Plated samples need annealing to improve the adhesion of electroless nickel.
Polymer: Polycarbonate (Laxan) plaque
Pre-etch Formulation: Enplate 3489:Water (75:25 v/v), 7 minutes, at RT
Etch Formulation: Sulfuric (55 ml.), and phosphoric (45 ml.), 10 minutes at RT
Electroless Nickel: As in Example 1.
Results: Excellent adhesion of electroless nickel. Passes thermal cycle test.
Polymer: Polycarbonate (Laxan) plaque
Pre-etch Formulation: Shipley PM 921 (prepared from dichloro propanol):Water (80:120 v/v,) 5 minutes at 45° C.
Etch #1 Formulation: Sulfuric (55 ml.), and phosphoric (45 ml.) 10 minutes at RT
Etch #2 Formulation: 10% NaOH 10 minutes at 60° C.
Electroless Nickel: As in Example 1.
Results: Excellent adhesion of electroless nickel.
Polymer: Polycarbonate (Laxan) plaque
Pre-etch Formulation: None
Etch Formulation: 20% Tetraethylammonium hydroxide in water 5 minutes at RT
Electroless Nickel: As in Example 1.
Results: Polymer is essentially unaffected by this etch. Adhesion of electroless nickel and electroless copper is poor.
Polymer: Polycarbonate (Laxan) plaque
Pre-etch Formulation: Shipley PM 921:water (80:120), 10 minutes at 45° C.
Etch Formulation: 25 ml of 20% Tetraethylammonium hydroxide in water.
10 minutes at 45° C.
Electroless copper: As in Example 1.
Results: Polymer surface wettable with excellent finish & adhesion of electroless copper. Passes thermal cycle test.
Polymer: Polycarbonate (Laxan) plaque
Pre-etch Formulation: Shipley PM 921:water (2:3), 10 minutes at 45° C.
Etch Formulation: 25 ml. of 20% Tetraethylammonium hydroxide in water and 10 ml. of isopropanol, 10 minutes at 45° C.
Electroless Copper: As in Example 1.
Results: Polymer surface wettable with excellent adhesion of electroless copper. Passes thermal cycle test.
Polymer: Polycarbonate (Laxan) plaque
Swelling/Etching Solution: Triethyelene glycol dimethyl ether:polyethyelene glycol (mol. wt. 200):tetraethylammonium hydroxide 25% solution (1:1:1) at 25° C. for 5 minutes.
Electroless Nickel: As described in Example 1.
Results: Wettable after 2 minute wash with hot water. Acceptable electroless nickel plating.
Polymer: Polycarbonate (Laxan) plaque
Swelling/Solution: Triethyelene glycol dimethylether:water:tetraethylammonium hydroxide 25% solution (8:1:1) plus two drops of Aliquot at 35° C. for 5 minutes.
Electroless Nickel: As described in Example 1.
Results: Good adhesion as electroless nickel.
Polymer: Polycarbonate (Laxan) plaque
Solution: Triethylene glycol dimethylether:water:tetraethylammonium hydroxide 25% solution (8:2:3) plus two drops of Aliquot at 40° C. for 5 minutes.
Electroless Nickel: As described in Example 1.
Results: Wettable surface and excellent adhesion of electroless nickel.
Polymer: Polycarbonate (Laxan) plaque
Step 1: Shipley pre-etch. 6 minutes at 45° C.
Step 2: 20% tetraethylammonium hydroxide in water at 60° C. for 5 minutes.
Electroless copper: As described in Example 1.
Results: Good adhesion of electroless copper.
Polymer: Polycarbonate (Laxan) plaque
Step 1: Shipley pre-etch. 6 minutes at 45° C.
Step 2: 20% choline hydroxide in water at 60° C. for 5 minutes.
Electroless copper: As described in Example 1.
Results: Good adhesion of electroless copper.
Polymer: Polycarbonate (Laxan) plaque
Step 1: Shipley pre-etch. 6 minutes at 45° C.
Step 2: 15% tetraethylammonium bromide+15% sodium hydroxide in water at 60° C. for 5 minutes.
Electroless copper: As described in Example 1.
Results: Good adhesion of electroless copper.
Polymer: Polycarbonate (Laxan) plaque
Step 1: Shipley pre-etch. 6 minutes at 45° C.
Step 2: 15% Choline chloride+15% sodium hydroxide in water at 60° C. for 5 minutes.
Electroless copper: As described in Example 1.
Results: Good adhesion of electroless copper.
Polymer: Polycarbonate (Laxan) plaque
Pre-etch: None
Swell/Etch: 20 ml Enthone pre-etch 3489+6 ml tetraethylammonium hydroxide (20% solution in water)+5 ml. isopropanol at 60° C. for 5 minutes.
Electroless copper: As described in Example 1.
Results: Good adhesion of electroless copper.
Polymer: Polycarbonate (Laxan) plaque
Step 1: 8:2 triethyleneglycol dimethylether:water, 5 minutes at RT
Step 2: 10:2.5:2 Aqueous 10% NaOH:Triethylene glycol dimethyl ether:polyethylene glycol (mol. wt. 200), 5 minutes at RT
Electroless Nickel: As described in Example 1.
Results: Good adhesion of electroless nickel.
Polymer: Polycarbonate (Laxan) plaque
Pre-etching System: Benzene sulfonic acid at 65° C.
Time: 2 minutes: Highly wettable surface
0.5 minute: Highly deglazed wettable surface.
Etching System: 10% KOH aqueous solution 10 minutes at 50° C.
Results: Benzene sulfonic acid provides wettable surface. The wettable surface can be plated with electroless nickel and copper with good adhesion.
Polymer: Polycarbonate plaque
Swelling/etching System: Molten benzene sulfonic acid at 65° C.
Time: 2 minutes: Highly wettable surface
0.5 minute: Highly deglazed wettable surface.
Results: Benzene sulfonic acid provides wettable surface. The wettable surface can be plated with electroless nickel and copper.
Polymer: Transparent polycarbonate (Laxan) sheet
Solution: Triethanolamine at 60° C.
Results: No effect.
Polymer: Transparent polycarbonate (Laxan) sheet
Solution: 50 ml 25% NaOH+25 ml triethanolamine, 10 minutes at 60° C.
Results: No effect.
Polymer: Polycarbonate (Laxan) plaque
Step 1: Enthone pre-etch 3489, 10 minutes at 45° C.
Step 2: 50 ml 25% NaOH+25 ml triethanolamine, 5 minutes at RT
Electroless nickel: As described in Example 1
Results: Good.
Polymer: Polycarbonate (Laxan) plaque
Etching Solution: Triethanolamine:Triethyelene glycol dimethylether:NaOH:water (2.5:4:1.5:10 v/v/w/v) at 50° C. for 5 minutes.
Electroless Nickel: As described in example 1
Results: White nickel. Good adhesion.
Polymer: Polycarbonate (Laxan FL-900 and 920A) panels
Pre-etching: Pre-etch with Enplate 3489:water (75:25)
Temperature: 75° F.,
Time: 10 minutes for FL-900 and 5 minutes for 920A
Rinses: (cold, hot and cold water rinses)
Etching: The formulations containing (1) Triethanolamine, TEA
(varied from 30-80%), (2) Sodium hydroxide (0.5-1.5N), and (3) Water (balance) were used.
Temperature: 150°-170° F.
Time: 10 minutes
Rinse: Cold, hot and cold water rinses
Electroless Plating:
(1) Pre-catalyst: Enplate 3923, 75° F., 2 min, cold water rinse (CWR)
(2) Catalyst: Enplate 850, 75° F., 5 min, CWR
(3) Accelerator: Enplate 860, 75° F., 5 min, CWR
(4) Electroless copper: Enplate 872, 75° F., 20 min, CWR
(5) Surface activation: Enplate 452, 75° F., 1 min, CWR
(6) Electroless nickel: Enplate 426, 150° F., 5 min, CWR
(7) Annealed at 170° F. for 30 min
Results: Plated samples were autoclaved five times at 12-15 psi for 30 minutes and then tested for adhesion with the ASTM cross-hatch test method between each autoclave. The results are summarized below (1 poor-5 excellent) after five cycles:
______________________________________ Initial After autoclave Concentration Conc. (N) of NaOH Conc. (N) of NaOH of TEA 0.5 1.0 1.5 0.5 1.0 1.5 ______________________________________ (A) Polycarbonate Laxan 920A panels etched at 170° F. ______________________________________ 30 2 5 5 1 2 2 40 2 5 5 1 2 2 50 4 5 5 3 5 5 60 5 5 5 4 5 5 70 5 5 5 5 5 5 80 5 5 5 5 5 -- ______________________________________ (B) Polycarbonate Laxan FL-900 panels etched at 170° F. ______________________________________ 30 2 5 5 1 4 5 40 3 5 5 2 3 4 50 5 5 5 4 5 4 60 -- 5 5 -- 3 5 70 5 5 5 4 5 5 80 5 5 5 4 4 -- ______________________________________ (C) Polycarbonate Laxan 920A panels etched at 150° F. ______________________________________ 30 3 5 5 2 4 3 40 2 5 5 1 5 5 50 3 5 5 2 5 5 60 4 5 5 5 5 5 70 5 5 5 5 5 5 80 5 5 5 5 5 5 ______________________________________ (D) Polycarbonate Laxan FL-900 panels at 150° F. ______________________________________ 30 3 5 5 1 4 5 40 4 5 5 1 3 5 50 5 5 5 2 4 5 60 5 5 5 2 5 5 70 5 5 4 5 5 5 80 5 5 5 5 5 5 ______________________________________
Polymer: Polycarbonate (Laxan) plaque
Etching Solution: Water:NaOH:Triethanolamine:Ethyleneglycol dimethylether (120:15:28:37 w:w:w:w) at 50° C. for 10 minutes
Electroless Nickel: As described in Example 1
Results: Good adhesion.
Polymer: Transparent polycarbonate (Laxan) sheet
Solution: Triethanolamine at RT
Results: Deglazes PC in 30 seconds
Polymer: Transparent polycarbonate (Laxan) sheet
Solution: TMEA:Triethanolamine:tetraethylammonium hydroxide (25%):water (6:3:2.5:2) at RT for 5 minutes at 50° C.
Electroless Nickel: As described in Example 1
Results: Good adhesion.
Polymer: Polystyrene plaque
Solution: 10% aqueous NaOH, Triethylene glycol dimethylether:polyethylene glycol (20:5:4), 10 minutes at 60° C.
Electroless Nickel: As described in Example 1.
Results: Extremely poor adhesion of electroless nickel.
Polymer: CR-39 plaque
Solution: 10% aqueous NaOH, Triethyelene glycol dimethylether:polyethylene glycol (20:5:4), 10 minutes at 60° C.
Electroless Nickel: As described in Example 1.
Results: Almost satisfactory adhesion of electroless nickel.
Polymer: Mylar (duPont)
Solution: 10% aqueous NaOH, Triethyelene glycol dimethylether:polyethylene glycol (20:5:4), 10 minutes at 60° C.
Electroless Nickel: As described in Example 1.
Results: Satisfactory adhesion of electroless nickel
Comment: Satisfactory adhesion of electroless nickel was obtained with another polyester, Dexloy-347.
Polymer: Mineral filled Nylon 6
Solution: 10% aqueous NaOH, Triethyelene glycol dimethylether:polyethylene glycol (20:5:4), 10 minutes at 60° C.
Electroless Nickel: As described in Example 1.
Results: Satisfactory adhesion of electroless nickel.
Polymer: Dow Pulse (an alloy of ABS and polycarbonate)
Solution: 10% aqueous NaOH, Triethyelene glycol dimethylether:polyethylene glycol (20:5:4), 10 minutes at 60° C.
Electroless Nickel: As described in Example 1.
Results: Satisfactory adhesion of electroless nickel.
Claims (13)
1. A process of two step surface etching of polymeric materials made of polymers having at least one hydrolyzable functionality selected from the group consisting of polycarbonates, anhydrides, carboxyl esters, sulphonic esters, amides and urethanes, which comprises
the first step of exposing the surface to be etched to a liquid phase capable of microroughening said surface, comprising a good solvent for said polymer and a non-solvent for said polymer provided that where at least one member of the group of said good and said non solvents etchant is immiscible with the other, said liquid phase further comprises a sufficient amount of solubilizing agent miscible with said immiscible components to provide a single liquid phase and
a second step of hydrolyzing the said functionalities on said surface to the extent needed to provide a water wettable surface capable of being plated with electroless nickel or electroless copper to provide a plated layer having a strong level of adhesion to said surface by treating said surface with an etchant selected from the group consisting of
acidic etchants selected from the group consisting of aqueous mineral acids free of metallic components, benzene sulphonic acid and mixtures thereof and
basic etchants selected from the group consisting of alkali metal hydroxides, quaternary ammonium hydroxides and mixtures thereof in the presence of an alkanolamine.
2. A process of claim 1, wherein the polymer is a polycarbonate.
3. A process of claim 1, wherein said good and said non solvents are immiscible and said liquid phase further comprises a solubilizing agent miscible with said good and said non solvents.
4. A process of claim 3, wherein the solubilizing agent is selected from the group consisting of lower alkanoic acids, lower alkylene glycols, lower alkanols and benzene sulphonic acid.
5. A process of claim 1, wherein the liquid phase comprises benzene sulphonic acid.
6. A process of claim 1, wherein the good solvent is selected from the group consisting of mono- or di-lower alkyl ethers of mono-, di- or tri-lower alkylene glycols.
7. A process of claim 6, wherein the good solvent is selected from the group consisting of mono- or di-methyl or ethyl ethers of mono-,di- or tri-ethylene glycol.
8. A process of claim 1, wherein the non-solvent is selected from the group consisting of water, lower alkylene glycols and lower alkanols.
9. A process of claim 1, wherein the etchant is a basic etchant in the presence of a wetting agent.
10. A process of claim 1, wherein the etchant is a basic etchant consisting essentially of triethanolamine and aqueous sodium hydroxide.
11. A process of claim 10, wherein the concentration of the triethanolamine is between 30 and 80% w/w of the etchant and the sodium hydroxide is 0.5 to 1.5N.
12. A process of claim 11, wherein the second step hydrolyzing reaction temperature is between 150° and 170° F.
13. A process of claim 12, wherein the polymer is a polycarbonate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/489,366 US5015329A (en) | 1988-11-07 | 1990-03-06 | Pre-swelling and etching of plastics for plating |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/268,154 US4941940A (en) | 1988-11-07 | 1988-11-07 | Pre-swelling and etching of plastics for plating |
US07/489,366 US5015329A (en) | 1988-11-07 | 1990-03-06 | Pre-swelling and etching of plastics for plating |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/268,154 Continuation US4941940A (en) | 1988-11-07 | 1988-11-07 | Pre-swelling and etching of plastics for plating |
Publications (1)
Publication Number | Publication Date |
---|---|
US5015329A true US5015329A (en) | 1991-05-14 |
Family
ID=26952907
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/489,366 Expired - Fee Related US5015329A (en) | 1988-11-07 | 1990-03-06 | Pre-swelling and etching of plastics for plating |
Country Status (1)
Country | Link |
---|---|
US (1) | US5015329A (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5176659A (en) * | 1991-02-28 | 1993-01-05 | Mario Mancini | Expandable intravenous catheter and method of using |
US5198096A (en) * | 1990-11-28 | 1993-03-30 | General Electric Company | Method of preparing polycarbonate surfaces for subsequent plating thereon and improved metal-plated plastic articles made therefrom |
US5385728A (en) * | 1993-09-28 | 1995-01-31 | Suh; Byoung I. | Antimicrobial etchants |
US5846665A (en) * | 1990-11-23 | 1998-12-08 | Lacks Industries, Inc. | Method for electroplating high-impact plastics |
US5928727A (en) * | 1997-06-02 | 1999-07-27 | Lacks Industries, Inc. | Method for electroplating elastomer-modified polyphthalamide articles |
US6141870A (en) * | 1997-08-04 | 2000-11-07 | Peter K. Trzyna | Method for making electrical device |
US20050199587A1 (en) * | 2004-03-12 | 2005-09-15 | Jon Bengston | Non-chrome plating on plastic |
US20060127653A1 (en) * | 2004-02-23 | 2006-06-15 | Guoping Mao | Chemical etching of polycarbonate films and related applications |
US20080171835A1 (en) * | 2007-01-16 | 2008-07-17 | Sulfo Technologies, Llc | Method of sulfonation of polymer substrate to impart a hydrophilic layer in said substrate with improvement in at least one of anti-fog, anti-static, wettability, lubricity anti-microbial properties, and articles made thereby |
WO2013112268A2 (en) | 2012-01-23 | 2013-08-01 | Macdermid Acumen, Inc. | Etching of plastic using acidic solutions containing trivalent manganese |
EP2657367A1 (en) * | 2012-04-24 | 2013-10-30 | Enthone Inc. | Pre-etching composition and etching process for plastic substrates |
US9534306B2 (en) | 2012-01-23 | 2017-01-03 | Macdermid Acumen, Inc. | Electrolytic generation of manganese (III) ions in strong sulfuric acid |
US9752241B2 (en) | 2012-01-23 | 2017-09-05 | Macdermid Acumen, Inc. | Electrolytic generation of manganese (III) ions in strong sulfuric acid using an improved anode |
KR20220034457A (en) * | 2020-09-11 | 2022-03-18 | 계명대학교 산학협력단 | A manufacturing method of metastructures for improving variablestiffness properties and wearable suit using it |
Citations (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3649391A (en) * | 1970-05-01 | 1972-03-14 | Albert D Lewis | Process for producing a marking receptive surface on a polystyrene substrate |
US3660293A (en) * | 1969-09-23 | 1972-05-02 | Crown City Plating Co | Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating |
US3671289A (en) * | 1969-09-23 | 1972-06-20 | Crown City Plating Co | Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating |
US3758332A (en) * | 1971-08-20 | 1973-09-11 | Western Electric Co | Method of metal coating an epoxy surface |
US3795622A (en) * | 1972-07-31 | 1974-03-05 | O Dutkewych | Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating |
US4042730A (en) * | 1976-03-29 | 1977-08-16 | Bell Telephone Laboratories, Incorporated | Process for electroless plating using separate sensitization and activation steps |
US4125649A (en) * | 1975-05-27 | 1978-11-14 | Crown City Plating | Pre-etch conditioning of polysulfone and other polymers for electroless plating |
US4216246A (en) * | 1977-05-14 | 1980-08-05 | Hitachi Chemical Company, Ltd. | Method of improving adhesion between insulating substrates and metal deposits electrolessly plated thereon, and method of making additive printed circuit boards |
US4268536A (en) * | 1978-12-07 | 1981-05-19 | Western Electric Company, Inc. | Method for depositing a metal on a surface |
US4281034A (en) * | 1980-04-03 | 1981-07-28 | Sunbeam Corporation | Plating on plastics by softening with trichloroethylene and methylene chloride bath |
US4297436A (en) * | 1974-12-26 | 1981-10-27 | Fuji Photo Film Co., Ltd. | Method for producing a multilayer printing plate |
EP0052968A2 (en) * | 1980-11-20 | 1982-06-02 | Crosfield Electronics Limited | Coating of polymerical substrates |
US4335164A (en) * | 1978-12-19 | 1982-06-15 | Crown City Plating Co. | Conditioning of polyamides for electroless plating |
EP0156120A2 (en) * | 1984-03-09 | 1985-10-02 | Allied Corporation | Method for pretreatment of polyesters for metal plating |
US4592929A (en) * | 1984-02-01 | 1986-06-03 | Shipley Company Inc. | Process for metallizing plastics |
US4594311A (en) * | 1984-10-29 | 1986-06-10 | Kollmorgen Technologies Corporation | Process for the photoselective metallization on non-conductive plastic base materials |
US4601916A (en) * | 1984-07-18 | 1986-07-22 | Kollmorgen Technologies Corporation | Process for bonding metals to electrophoretically deposited resin coatings |
WO1987000391A1 (en) * | 1985-06-24 | 1987-01-15 | Enthone, Incorporated | Process for conditioning the surface of plastic substrates prior to metal plating |
US4725504A (en) * | 1987-02-24 | 1988-02-16 | Polyonics Corporation | Metal coated laminate products made from textured polyimide film |
US4775557A (en) * | 1987-11-09 | 1988-10-04 | Enthone, Incorporated | Composition and process for conditioning the surface of polycarbonate resins prior to metal plating |
US4803097A (en) * | 1987-04-20 | 1989-02-07 | Allied-Signal Inc. | Metal plating of plastic materials |
EP0309243A1 (en) * | 1987-09-25 | 1989-03-29 | Engelhard Technologies Limited | Pre-etch treatment of a plastics substrate |
US4832799A (en) * | 1987-02-24 | 1989-05-23 | Polyonics Corporation | Process for coating at least one surface of a polyimide sheet with copper |
EP0317748A2 (en) * | 1987-11-25 | 1989-05-31 | Schering Aktiengesellschaft | Pre-treatment process for synthetic resins |
US4873136A (en) * | 1988-06-16 | 1989-10-10 | General Electric Company | Method for preparing polymer surfaces for subsequent plating thereon, and improved metal-plated plastic articles made therefrom |
US4895739A (en) * | 1988-02-08 | 1990-01-23 | Shipley Company Inc. | Pretreatment for electroplating process |
US4941940A (en) * | 1988-11-07 | 1990-07-17 | Jp Laboratories, Inc. | Pre-swelling and etching of plastics for plating |
-
1990
- 1990-03-06 US US07/489,366 patent/US5015329A/en not_active Expired - Fee Related
Patent Citations (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3660293A (en) * | 1969-09-23 | 1972-05-02 | Crown City Plating Co | Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating |
US3671289A (en) * | 1969-09-23 | 1972-06-20 | Crown City Plating Co | Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating |
US3649391A (en) * | 1970-05-01 | 1972-03-14 | Albert D Lewis | Process for producing a marking receptive surface on a polystyrene substrate |
US3758332A (en) * | 1971-08-20 | 1973-09-11 | Western Electric Co | Method of metal coating an epoxy surface |
US3795622A (en) * | 1972-07-31 | 1974-03-05 | O Dutkewych | Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating |
US4297436A (en) * | 1974-12-26 | 1981-10-27 | Fuji Photo Film Co., Ltd. | Method for producing a multilayer printing plate |
US4125649A (en) * | 1975-05-27 | 1978-11-14 | Crown City Plating | Pre-etch conditioning of polysulfone and other polymers for electroless plating |
US4042730A (en) * | 1976-03-29 | 1977-08-16 | Bell Telephone Laboratories, Incorporated | Process for electroless plating using separate sensitization and activation steps |
US4216246A (en) * | 1977-05-14 | 1980-08-05 | Hitachi Chemical Company, Ltd. | Method of improving adhesion between insulating substrates and metal deposits electrolessly plated thereon, and method of making additive printed circuit boards |
US4268536A (en) * | 1978-12-07 | 1981-05-19 | Western Electric Company, Inc. | Method for depositing a metal on a surface |
US4335164A (en) * | 1978-12-19 | 1982-06-15 | Crown City Plating Co. | Conditioning of polyamides for electroless plating |
US4281034A (en) * | 1980-04-03 | 1981-07-28 | Sunbeam Corporation | Plating on plastics by softening with trichloroethylene and methylene chloride bath |
EP0052968A2 (en) * | 1980-11-20 | 1982-06-02 | Crosfield Electronics Limited | Coating of polymerical substrates |
US4592929A (en) * | 1984-02-01 | 1986-06-03 | Shipley Company Inc. | Process for metallizing plastics |
EP0156120A2 (en) * | 1984-03-09 | 1985-10-02 | Allied Corporation | Method for pretreatment of polyesters for metal plating |
US4601916A (en) * | 1984-07-18 | 1986-07-22 | Kollmorgen Technologies Corporation | Process for bonding metals to electrophoretically deposited resin coatings |
US4594311A (en) * | 1984-10-29 | 1986-06-10 | Kollmorgen Technologies Corporation | Process for the photoselective metallization on non-conductive plastic base materials |
WO1987000391A1 (en) * | 1985-06-24 | 1987-01-15 | Enthone, Incorporated | Process for conditioning the surface of plastic substrates prior to metal plating |
US4832799A (en) * | 1987-02-24 | 1989-05-23 | Polyonics Corporation | Process for coating at least one surface of a polyimide sheet with copper |
US4725504A (en) * | 1987-02-24 | 1988-02-16 | Polyonics Corporation | Metal coated laminate products made from textured polyimide film |
US4803097A (en) * | 1987-04-20 | 1989-02-07 | Allied-Signal Inc. | Metal plating of plastic materials |
EP0309243A1 (en) * | 1987-09-25 | 1989-03-29 | Engelhard Technologies Limited | Pre-etch treatment of a plastics substrate |
US4775557A (en) * | 1987-11-09 | 1988-10-04 | Enthone, Incorporated | Composition and process for conditioning the surface of polycarbonate resins prior to metal plating |
EP0317748A2 (en) * | 1987-11-25 | 1989-05-31 | Schering Aktiengesellschaft | Pre-treatment process for synthetic resins |
US4895739A (en) * | 1988-02-08 | 1990-01-23 | Shipley Company Inc. | Pretreatment for electroplating process |
US4873136A (en) * | 1988-06-16 | 1989-10-10 | General Electric Company | Method for preparing polymer surfaces for subsequent plating thereon, and improved metal-plated plastic articles made therefrom |
US4941940A (en) * | 1988-11-07 | 1990-07-17 | Jp Laboratories, Inc. | Pre-swelling and etching of plastics for plating |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5846665A (en) * | 1990-11-23 | 1998-12-08 | Lacks Industries, Inc. | Method for electroplating high-impact plastics |
US5198096A (en) * | 1990-11-28 | 1993-03-30 | General Electric Company | Method of preparing polycarbonate surfaces for subsequent plating thereon and improved metal-plated plastic articles made therefrom |
US5176659A (en) * | 1991-02-28 | 1993-01-05 | Mario Mancini | Expandable intravenous catheter and method of using |
US5385728A (en) * | 1993-09-28 | 1995-01-31 | Suh; Byoung I. | Antimicrobial etchants |
US5928727A (en) * | 1997-06-02 | 1999-07-27 | Lacks Industries, Inc. | Method for electroplating elastomer-modified polyphthalamide articles |
US20090196980A1 (en) * | 1997-08-04 | 2009-08-06 | Mcdermott Brian J | Electrical device with teeth joining layers and method for making the same |
US8581105B2 (en) | 1997-08-04 | 2013-11-12 | Brian J. McDermott | Electrical device with teeth joining layers and method for making the same |
US8278560B2 (en) | 1997-08-04 | 2012-10-02 | Mcdermott Brian J | Electrical device with teeth joining layers and method for making the same |
US6141870A (en) * | 1997-08-04 | 2000-11-07 | Peter K. Trzyna | Method for making electrical device |
US9374912B2 (en) | 1997-08-04 | 2016-06-21 | Continental Circuits LLC | Electrical device with teeth joining layers and method for making the same |
US20060127653A1 (en) * | 2004-02-23 | 2006-06-15 | Guoping Mao | Chemical etching of polycarbonate films and related applications |
US20050199587A1 (en) * | 2004-03-12 | 2005-09-15 | Jon Bengston | Non-chrome plating on plastic |
US20080171835A1 (en) * | 2007-01-16 | 2008-07-17 | Sulfo Technologies, Llc | Method of sulfonation of polymer substrate to impart a hydrophilic layer in said substrate with improvement in at least one of anti-fog, anti-static, wettability, lubricity anti-microbial properties, and articles made thereby |
EP3406763A1 (en) | 2012-01-23 | 2018-11-28 | MacDermid Acumen, Inc. | Etching of plastic using acidic solutions containing trivalent manganese |
US9534306B2 (en) | 2012-01-23 | 2017-01-03 | Macdermid Acumen, Inc. | Electrolytic generation of manganese (III) ions in strong sulfuric acid |
US9752241B2 (en) | 2012-01-23 | 2017-09-05 | Macdermid Acumen, Inc. | Electrolytic generation of manganese (III) ions in strong sulfuric acid using an improved anode |
WO2013112268A2 (en) | 2012-01-23 | 2013-08-01 | Macdermid Acumen, Inc. | Etching of plastic using acidic solutions containing trivalent manganese |
US10221357B2 (en) | 2012-01-23 | 2019-03-05 | Macdermid Acumen, Inc. | Etching of plastic using acidic solutions containing trivalent manganese |
US10246788B2 (en) | 2012-01-23 | 2019-04-02 | Macdermid Acumen, Inc. | Electrolytic generation of manganese (III) ions in strong sulfuric acid using an improved anode |
US10260000B2 (en) | 2012-01-23 | 2019-04-16 | Macdermid Acumen, Inc. | Etching of plastic using acidic solutions containing trivalent manganese |
US10280367B2 (en) | 2012-01-23 | 2019-05-07 | Macdermid Acumen, Inc. | Etching of plastic using acidic solutions containing trivalent manganese |
US10895016B2 (en) | 2012-01-23 | 2021-01-19 | Macdermid Acumen, Inc. | Electrolytic generation of manganese (III) ions in strong sulfuric acid |
WO2013163316A3 (en) * | 2012-04-24 | 2014-06-12 | Enthone Inc. | Pre-etching composition and etching process for plastic substrates |
EP2657367A1 (en) * | 2012-04-24 | 2013-10-30 | Enthone Inc. | Pre-etching composition and etching process for plastic substrates |
KR20220034457A (en) * | 2020-09-11 | 2022-03-18 | 계명대학교 산학협력단 | A manufacturing method of metastructures for improving variablestiffness properties and wearable suit using it |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4941940A (en) | Pre-swelling and etching of plastics for plating | |
US5015329A (en) | Pre-swelling and etching of plastics for plating | |
US5049230A (en) | Single step pre-swelling and etching of plastics for plating | |
KR960003735B1 (en) | Composition and process for conditioning the surface of polycarbonate resins prior to metal plating | |
US4086128A (en) | Process for roughening surface of epoxy resin | |
US5167992A (en) | Selective electroless plating process for metal conductors | |
CA1265698A (en) | Process for the photoselective metallization on non- conductive plastic base materials | |
US4832799A (en) | Process for coating at least one surface of a polyimide sheet with copper | |
US4099974A (en) | Electroless copper solution | |
EP0280502A1 (en) | Metal coated laminate products from textured polyimide film | |
US4592929A (en) | Process for metallizing plastics | |
EP0832918A1 (en) | Resin etching solution and etching process | |
US5180639A (en) | Method of preparing polymer surfaces for subsequent plating thereon and improved metal-plated plastic articles made therefrom | |
EP0261424B1 (en) | Metal plating process | |
US4806395A (en) | Textured polyimide film | |
US5019425A (en) | Process for the pre-treatment of synthetic materials | |
EP2712885A1 (en) | A method for electroless metallization | |
EP2845923A1 (en) | Electroless metallization of dielectrics with alkaline stable pyrazine derivative containing catalysts | |
US4820548A (en) | Three step process for treating plastics with alkaline permanganate solutions | |
US5591354A (en) | Etching plastics with nitrosyls | |
US5591488A (en) | Process for treating plastic surfaces and swelling solution | |
US20050042383A1 (en) | Colloidal seed formation for printed circuit board metallization | |
US4431685A (en) | Decreasing plated metal defects | |
AU575953B2 (en) | Composition and process for conditioning the surface of plastic substrates prior to metal plating | |
AU580433B2 (en) | Process for conditioning the surface of plastic substrates prior to metal plating |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19990514 |
|
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |